JP2022180911A - Method for producing complex and complex - Google Patents

Abstract

To provide a method for producing readily a complex having excellent dispersibility of microfibrillated vegetable fiber, a complex, a rubber composition and a tire.SOLUTION: A method for producing a complex includes a step 1 for mixing microfibrillated vegetable fiber, a cationic surfactant having cationic nitrogen and water to make a mixture 1, a step 2 for mixing the mixture 1 and an alcohol to make a mixture 2, a step 3 for mixing the mixture 2 and a plasticizer to make a mixture 3, and a step 4 for drying the mixture 3 to make a complex containing the microfibrillated vegetable fiber and the plasticizer.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing a composite, a composite, a rubber composition, and a tire.

As a technique for dispersing microfibrillated plant fibers such as cellulose fibers in polymers such as rubber, a water-dispersed slurry of microfibrillated plant fibers is mixed with rubber latex, and then coagulated, dehydrated, and dried to produce a composite. A wet masterbatch method (WMB method) has been proposed. However, since the WMB method uses a low-concentration microfibrillated plant fiber (concentration of microfibrillated plant fiber of 1% by mass, etc.), there is a problem that transportation and manufacturing costs are high.

An object of the present invention is to solve the above-mentioned problems and to provide a method for producing a composite, a composite, a rubber composition, and a tire by which a composite having excellent dispersibility of microfibrillated plant fibers can be easily produced. .

The present invention comprises a step 1 of mixing microfibrillated plant fibers, a cationic surfactant having cationic nitrogen and water to prepare a mixture 1;
Step 2 of mixing the mixture 1 and alcohol to prepare a mixture 2;
Step 3 of mixing the mixture 2 and a plasticizer to produce a mixture 3;
and a step 4 of drying the mixture 3 to produce a composite containing the microfibrillated plant fibers and the plasticizer.

In step 1, it is preferable that an aqueous solution of microfibrillated plant fibers containing 0.1 to 20% by mass of microfibrillated plant fibers is used and mixed using a homogenizer.

It is preferable to further perform dehydration under reduced pressure using a suction filtration device after the step 1 to adjust the solid content of the mixture 1 to 10% by mass or more.

It is preferable to further perform dehydration under reduced pressure using a suction filtration device after the step 2 to adjust the solid content of the mixture 2 to 20% by mass or more.

Preferably, the plasticizer contains a glycerol fatty acid triester.

The step 4 preferably adjusts the solid content of the obtained composite to 90% by mass or more.

In step 1, the amount of the cationic surfactant having cationic nitrogen added to 100 parts by mass (solid content) of the microfibrillated plant fibers is preferably 10 to 35 parts by mass.

The cationic surfactant having cationic nitrogen preferably contains at least one selected from the group consisting of quaternary ammonium salts and alkylamine salts.

In step 2, the amount of the alcohol added to 100 parts by mass (solid content) of the microfibrillated plant fibers is preferably 2,000 to 10,000 parts by mass.

In step 3, the amount of the plasticizer added to 100 parts by mass (solid content) of the microfibrillated plant fibers is preferably 70 to 300 parts by mass.

TECHNICAL FIELD The present invention relates to a powdery composite obtained by mixing microfibrillated plant fibers having an average fiber diameter of 10 μm or less and a plasticizer and drying the mixture.

In the composite, the plasticizer preferably contains vegetable oil.

The composite preferably contains a vegetable oil having an iodine value of 60 or more and 160 or less as the plasticizer.

The composite preferably contains a vegetable oil as the plasticizer and satisfies the following formula.
Microfibrillated vegetable fiber content (mass%) / (vegetable oil content (mass%) × iodine value of vegetable oil) ≤ 0.0100

The composite is preferably an additive for a rubber composition or a resin composition.

The present invention relates to a rubber composition for tires obtained by mixing the composite with a rubber component.

The present invention relates to a tire comprising a member made of the rubber composition.

The present invention comprises a step 1 of mixing microfibrillated plant fibers, a cationic surfactant having cationic nitrogen and water to prepare a mixture 1, and a step of mixing the mixture 1 and alcohol to prepare a mixture 2. 2, a step 3 of mixing the mixture 2 and the plasticizer to prepare a mixture 3, and a step 4 of drying the mixture 3 to prepare a composite comprising the microfibrillated plant fiber and the plasticizer. Since it is a method for producing a composite containing, a composite having excellent dispersibility of microfibrillated plant fibers can be easily produced.

<Method for producing composite>
The present invention comprises a step 1 of mixing microfibrillated plant fibers, a cationic surfactant having cationic nitrogen and water to prepare a mixture 1, and a step of mixing the mixture 1 and alcohol to prepare a mixture 2. 2, a step 3 of mixing the mixture 2 and the plasticizer to prepare a mixture 3, and a step 4 of drying the mixture 3 to prepare a composite comprising the microfibrillated plant fiber and the plasticizer. A method for producing a composite comprising Although the production method is a simple production method, it can satisfactorily produce a composite having excellent dispersibility of microfibrillated plant fibers.

Although the mechanism by which such effects are obtained is not clear, it is speculated as follows.
First, in step 1, microfibrillated plant fibers having a strong cohesive force are mixed with a cationic surfactant having cationic nitrogen to prevent aggregation of the microfibrillated plant fibers. Furthermore, by further mixing the alcohol in step 2 and the plasticizer in step 3, the compatibility between the microfibrillated plant fibers and the plasticizer is improved, and aggregation of the microfibrillated plant fibers is further prevented. Then, in step 4, by drying the mixture 3 containing the microfibrillated plant fibers and the plasticizer in such an aggregation-prevented state, the microfibrillated plant fibers are sufficiently prevented from aggregation. It is believed that a composite is created that includes the plant fiber and the plasticizer. Therefore, it is presumed that, in spite of such a simple production method, it is possible to produce a composite having excellent dispersibility of microfibrillated plant fibers.

(Step 1)
In step 1, a mixture 1 is prepared by mixing microfibrillated plant fibers, a cationic surfactant having cationic nitrogen, and water.

Cellulose microfibrils are preferable as microfibrillated plant fibers from the viewpoint of breaking strength, abrasion resistance, and the like. Cellulose microfibrils are not particularly limited as long as they are derived from natural products. Examples include resource biomass such as fruits, grains, and root vegetables, wood, bamboo, hemp, jute, kenaf, and pulp obtained from these as raw materials. In addition to waste biomass such as paper, cloth, agricultural waste, food waste and sewage sludge, unused biomass such as rice straw, wheat straw, and thinned wood, those derived from cellulose produced by sea squirts, acetic acid bacteria, etc. be done. These microfibrillated plant fibers may be used singly or in combination of two or more.

In this specification, cellulose microfibrils typically refer to cellulose fibers having an average fiber diameter of several tens of μm (20 to 30 μm or less), preferably 10 μm or less, and more typically cellulose microfibrils. means a cellulose fiber (microfibrillated plant fiber with an average fiber diameter of several tens of μm or less, 10 μm or less, or 500 nm or less) having a microstructure formed by aggregation of cellulose molecules and having an average fiber diameter of 500 nm or less. In addition, typical cellulose microfibrils can be formed, for example, as aggregates of cellulose fibers having an average fiber diameter as described above.

The method for producing microfibrillated plant fibers is not particularly limited. ), mechanical grinding or beating using a twin-screw kneading extruder, high-pressure homogenizer, medium stirring mill, stone mill, grinder, vibration mill, sand grinder, or the like. In these methods, lignin is separated from the raw material by chemical treatment, resulting in microfibrillated plant fibers substantially free of lignin. Moreover, as another method, a method of subjecting a raw material of cellulose microfibrils to ultra-high pressure treatment and the like can be mentioned.

As microfibrillated plant fibers, for example, products of Sugino Machine Co., Ltd., Daicel Finechem Co., Ltd., etc. can be used.

As described above, even unmodified microfibrillated plant fibers obtained by the above production method can be sufficiently oriented in the polymer. In addition to fibrillated plant fibers, those subjected to oxidation treatment and various chemical modification treatments, etc., and natural products that can be derived from cellulose microfibrils (for example, wood, pulp, bamboo, hemp, jute, kenaf, agricultural waste, Cloth, paper, sea squirt cellulose, etc.) can be used as a cellulose raw material, subjected to oxidation treatment and various chemical denaturation treatments, and then defibrated if necessary (chemically denatured microfibrillated plant fibers, etc. ).

Examples of chemical modification of microfibrillated plant fibers include esterification treatment, etherification treatment, and acetalization treatment. Specifically, acylation such as acetylation, cyanoethylation, amination, sulfoneesterification, phosphate esterification, alkylesterification, alkyletherification, complex esterification, β-ketoesterification, and alkylation such as butylation. , chlorination, and the like are preferably exemplified. Furthermore, alkyl carbamate-ization and aryl carbamate-ization can also be exemplified.

Chemically modified microfibrillated plant fibers are preferably chemically modified so that the degree of substitution is within the range of 0.2 to 2.5. Here, the degree of substitution means the average number of hydroxyl groups per glucose ring unit substituted with other functional groups by chemical modification among the hydroxyl groups of cellulose, and the theoretical maximum value is 3. The degree of substitution is more preferably in the range of 0.3 to 2.5, more preferably in the range of 0.5 to 2.3, and in the range of 0.5 to 2.0 It is particularly preferred to have When the chemically modified microfibrillated plant fibers are a combination of two or more, the degree of substitution is calculated as an average of the chemically modified microfibrillated plant fibers as a whole.

The degree of substitution in chemically modified microfibrillated plant fibers can be confirmed by, for example, titration using 0.5N-NaOH and 0.2N-HCl, NMR, infrared absorption spectroscopy, and the like.

Suitable chemically modified microfibrillated plant fibers include aminated microfibrillated plant fibers having a degree of substitution within the range of 0.3 to 2.5. The degree of substitution is preferably 0.3 to 2.0, more preferably 0.5 to 2.3, still more preferably 0.7 to 2.0, and particularly preferably 0.9 to 1.8.

When the chemically modified microfibrillated plant fibers are acetylated microfibrillated plant fibers, the degree of substitution is 0.3 to 2.5, and when the sulfone-esterified microfibrillated plant fibers are used, the degree of substitution is 0.3 to 1.8. , In the case of alkyl-esterified microfibril cellulose, the degree of substitution is 0.3 to 1.8; in the case of composite esterified microfibril cellulose, the degree of substitution is 0.4 to 1.8; has a degree of substitution of 0.3 to 1.8, an alkyl carbamate-modified microfibril cellulose has a degree of substitution of 0.3 to 1.8, and an aryl carbamate-modified microfibril cellulose has a degree of substitution of 0.3 to 1.8. Within the range of 8 is preferred.

Acetylation can be carried out, for example, by adding acetic acid, concentrated sulfuric acid, or acetic anhydride to microfibrillated plant fibers and allowing them to react. Specifically, for example, in a mixed solvent of acetic acid and toluene, in the presence of a sulfuric acid catalyst, microfibrillated plant fibers are reacted with acetic anhydride to proceed with the acetylation reaction, and then the solvent is replaced with water. etc., can be carried out by a conventionally known method.

Amination is performed by, for example, oxidation treatment using an N-oxyl compound such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), followed by, for example, alcohol (e.g., carbon such as ethanol). In an alcohol having 1 to 10 carbon atoms (preferably an alcohol having 1 to 5 carbon atoms, more preferably a primary alcohol having 1 to 4 carbon atoms), an amine compound (for example, a C 1 to 30 alcohol such as oleylamine) A primary amine compound (preferably a primary amine compound having 3 to 25 carbon atoms having a saturated or unsaturated bond, more preferably a primary amine compound having 6 to 23 carbon atoms having an unsaturated bond, still more preferably Primary amine compound having 10 to 20 carbon atoms having an unsaturated double bond)) and quaternary alkylammonium salts (preferably quaternary alkylammonium salts having 1 to 30 carbon atoms, more preferably hexadecyltrimethylammonium) It can be carried out by a known method such as a method of reacting with a quaternary alkylammonium halide having 1 to 20 carbon atoms such as chloride to carry out a nucleophilic substitution reaction, or a tosyl esterification method.

Sulfone-esterification can be carried out by a simple operation of, for example, dissolving microfibrillated plant fibers in sulfuric acid and putting the solution into water. In addition, it can be carried out by a method of treating with anhydrous sulfuric acid gas, a method of treating with chlorosulfonic acid and pyridine, or the like.

Phosphate esterification can be carried out, for example, by a method of treating microfibrillated plant fibers treated with dimethylamine or the like with phosphoric acid and urea.

Alkyl esterification can be performed, for example, by the Schotten-Baumann method (Schotten-Baumann method) in which microfibrillated plant fibers are reacted with carboxylic acid chloride under basic conditions. Williamson's method or the like, in which fibrillated plant fibers are reacted with an alkyl halide under basic conditions, can be used.

Chlorination can be carried out, for example, by adding thionyl chloride in DMF (dimethylformamide) and heating.

Complex esterification can be carried out, for example, by reacting microfibrillated plant fibers with two or more kinds of carboxylic acid anhydrides or carboxylic acid chlorides under basic conditions.

β-Ketoesterification can be carried out, for example, by reacting microfibrillated plant fibers with diketene or alkylketene dimer, or by transesterifying microfibrillated plant fibers and β-ketoester compounds such as alkylacetoacetate. .

Alkyl carbamate formation can be carried out, for example, by a method of reacting microfibrillated plant fibers with an alkyl isocyanate in the presence of a basic catalyst or a tin catalyst.

Aryl carbamate formation can be carried out, for example, by a method of reacting microfibrillated plant fibers with aryl isocyanate in the presence of a basic catalyst or a tin catalyst.

In step 1, a cationic surfactant with a cationic nitrogen is used. Here, the cationic nitrogen contained in the cationic surfactant refers to a nitrogen atom in the surfactant that can become a positively charged nitrogen atom under the environment in which the production method is carried out. By using a cationic surfactant having a cationic nitrogen, an interaction occurs between the hydrophilic side of the cationic surfactant and the microfibrillated plant fibers, and the plasticizer and the hydrophobic side to be mixed in a later step It is thought that a composite containing microfibrillated plant fibers with excellent dispersibility and a plasticizer can be obtained by interaction between.

Cationic surfactants having a cationic nitrogen that can be used in step 1 include quaternary ammonium salts, alkylamine salts, and the like. Among them, quaternary ammonium salts are preferable from the viewpoint of obtaining more effects.

Examples of the quaternary ammonium salts include quaternary ammonium salts having one or two alkyl groups having 11 to 23 carbon atoms. Specific examples include quaternary ammonium salts represented by the following general formula (1).

[In the formula, R ¹ represents an alkyl group having 11 to 23 carbon atoms. R ² represents an alkyl group having 1 to 25 carbon atoms or a benzyl group. R ³ and R ⁴ each represent an alkyl group having 1 to 4 carbon atoms. X ⁻ denotes an anion. ]

In general formula (1), R ¹ is preferably an alkyl group having 12 or more and 18 or less carbon atoms.
In general formula (1), the alkyl group for R ² preferably has 1 or more and 10 or less carbon atoms. R ² is more preferably an alkyl group having 1 to 18 carbon atoms or a benzyl group, and more preferably an alkyl group having 1 to 10 carbon atoms.
In general formula (1), each of R ³ and R ⁴ is preferably an alkyl group having 1 or 2 carbon atoms.
In general formula (1), X ⁻ is preferably a chloride ion (Cl ⁻ ).

Specific examples of quaternary ammonium salts include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, and alkyl (11 to 23 carbon atoms) benzyldimethylammonium chloride. Among them, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, and distearyldimethylammonium chloride are preferred, and stearyltrimethylammonium chloride and distearyldimethylammonium chloride are more preferred, from the viewpoint of obtaining more effects.

Commercially available quaternary ammonium salts include Cortamine 24P, Cortamine 60W, Cortamine 86P Conc, Cortamine 86W, Cortamine D86P, Sansol C, and Sansol B-50 (all manufactured by Kao Corporation).

Examples of alkylamine salts include alkylamine salts having an alkyl group having from 11 to 23 carbon atoms (for example, salts are acetates).

Specific examples of alkylamine salts include coconutamine acetate and stearylamine acetate.

Commercially available alkylamine salts include Acetamine 24 and Acetamine 86 (both manufactured by Kao Corporation).

Water that can be used in step 1 is not particularly limited, and examples thereof include tap water, ion-exchanged water (deionized water), and distilled water. These may be used alone or in combination of two or more. Among them, ion-exchanged water is preferable. Water can be mixed in various ways, such as being separately blended as a material other than the microfibrillated plant fibers and the cationic surfactant having cationic nitrogen, or being blended as a material contained in the microfibrillated plant fiber aqueous solution described below. However, it is particularly preferable to incorporate it as a material contained in the aqueous solution of microfibrillated plant fibers.

In the preparation of the mixture 1 containing the microfibrillated plant fibers, the cationic surfactant having cationic nitrogen, and water in step 1, from the viewpoint of obtaining more effects, the microfibrillated plant fibers are dispersed in water. (Microfibrillated vegetable fiber aqueous solution) is preferably mixed with other materials.

The microfibrillated plant fiber aqueous solution can be produced by a known method, for example, by dispersing microfibrillated plant fibers in water using a homogenizer (high-speed homogenizer, ultrasonic homogenizer, etc.), colloid mill, blender mill, or the like. can be prepared. The temperature and time during preparation can also be appropriately set so that the microfibrillated plant fibers are sufficiently dispersed in water.

The microfibrillated plant fiber content (solid content) in the microfibrillated plant fiber aqueous solution is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.5% by mass or more. and is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 3.0% by mass or less, and particularly preferably 1.0% by mass or less.

Step 1 of mixing microfibrillated plant fibers, a cationic surfactant having cationic nitrogen, and water to prepare a mixture 1 containing these components can be performed by a known mixing method. For example, microfibrillated plant fibers, cationic surfactants containing cationic nitrogen, water are mixed with a known Mixture 1 can be prepared by mixing and dispersing in a method. The temperature and time during the preparation can be appropriately set within a range normally practiced so that the microfibrillated plant fibers are sufficiently dispersed, or can be adjusted as appropriate while measuring the viscosity so that the mixture has a desired viscosity. For example, the temperature is preferably 5 to 80°C, more preferably 10 to 50°C, even more preferably 12 to 40°C.

In the step 1 of mixing the microfibrillated plant fibers, the cationic surfactant having cationic nitrogen, and water, from the viewpoint of obtaining more effects, the cation per 100 parts by mass (solid content) of the microfibrillated plant fibers The addition amount of the cationic surfactant having a nitrogenous nitrogen is preferably in the range of 0.1 to 50 parts by mass. The lower limit is more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more. The upper limit is more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, and particularly preferably 30 parts by mass or less.

After step 1, the mixture 1 obtained in step 1 is preferably further subjected to a dehydration treatment.
As the dehydration treatment, for example, general treatment methods such as suction dehydration and centrifugal dehydration can be adopted. Among them, the dehydration treatment is preferably dehydration under reduced pressure using a suction filtration device.

From the viewpoint of obtaining more effects, it is preferable to adjust the solid content of mixture 1 (100% by mass) to 5% by mass or more, more preferably 7% by mass or more, and further by dehydration treatment after step 1. It is preferably 9% by mass or more, particularly preferably 10% by mass or more. Although the upper limit is not particularly limited, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

(Step 2)
In step 2, mixture 2 is prepared by mixing alcohol with mixture 1, which has been dehydrated as necessary, as described above.

As the alcohol that can be used in step 2, known alcohol compounds can be used, and examples thereof include linear, branched or cyclic alkyl alcohols or alkoxy alcohols, aromatic alcohols, fluoroalcohols, and the like. The alkyl alcohol preferably has 1 to 25 carbon atoms, the alkoxy alcohol preferably has 1 to 10 carbon atoms, the aromatic alcohol preferably has 6 to 10 carbon atoms, and the fluoroalcohol preferably has 1 to 6 carbon atoms. is preferred. Among them, linear, branched or cyclic alkyl alcohols are preferable, and linear alkyl alcohols are more preferable.

Alkyl alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, hexadecanol, octadecanol, eicosanol, docosanol, and the like. Alkoxy alcohols include methoxyethanol, ethoxyethanol, and the like. Aromatic alcohols include benzyl alcohol, 2-benzyloxyethanol, and the like. Fluoroalcohols include perfluoroalcohols such as perfluoroethanol; 2-fluoroethanol, 2,2,2-trifluoroethanol and the like. Among them, ethanol, propanol and butanol are preferred, and ethanol is more preferred. These may be used alone or in combination of two or more.

Mixture 1, which has been subjected to dehydration treatment as necessary, and alcohol are mixed to prepare mixture 2 containing these components. A similar method can be adopted. The temperature and time during preparation can be appropriately set within the range usually performed, or can be adjusted as appropriate while measuring the viscosity so that the mixture has a desired viscosity. For example, the temperature is preferably 5 to 80°C, more preferably 10 to 50°C, even more preferably 12 to 40°C.

In the step 2 of mixing alcohol with the mixture 1 which has been optionally dehydrated, the amount of alcohol added to 100 parts by mass (solid content) of microfibrillated plant fibers is 100 to 100, from the viewpoint of obtaining more effects. A range of 50,000 parts by mass is preferred. The lower limit is more preferably 1000 parts by mass or more, still more preferably 2000 parts by mass or more, and particularly preferably 3000 parts by mass or more. The upper limit is more preferably 20000 parts by mass or less, still more preferably 10000 parts by mass or less, and particularly preferably 8000 parts by mass or less.

After step 2, it is preferable to further dehydrate the mixture 2 obtained in step 2.
As the dehydration treatment, a known method can be used, for example, the same method as the method after step 1 can be adopted. Among them, the dehydration treatment is preferably dehydration under reduced pressure using a suction filtration device.

From the viewpoint of obtaining a better effect, the dehydration treatment after step 2 preferably makes the solid content of mixture 2 (100% by mass) 12% by mass or more, more preferably 15% by mass or more, and even more preferably. is 18% by mass or more, particularly preferably 20% by mass or more. Although the upper limit is not particularly limited, it is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

(Step 3)
In step 3, mixture 3 is prepared by mixing mixture 2, optionally dehydrated, with a plasticizer, as described above.

As used herein, a plasticizer is a material that imparts plasticity to rubber and/or resin, and includes liquid plasticizers (liquid (liquid) plasticizers at 25°C) and solid plasticizers (solid plasticizers at 25°C). agent). Among them, liquid plasticizers are preferable from the viewpoint of obtaining more effects. Plasticizers may be used alone or in combination of two or more.

Liquid plasticizers that can be used in step 2 are not particularly limited, and include oils, liquid resins, liquid diene-based polymers, and the like. Among them, oil is preferable from the viewpoint of obtaining more effects.

Oils that can be used in Step 2 are not particularly limited and include, for example, known oils such as process oils, vegetable oils, or mixtures thereof.
Examples of process oils that can be used include paraffinic process oils, aromatic process oils, naphthenic process oils, and low PCA (polycyclic aromatic) process oils such as TDAE and MES. Vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil (canola oil), soybean oil, palm oil, coconut oil, peanut oil, rosin, pine oil, pine tar, tall oil, corn oil, rice bran oil, and safflower oil. , sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, macadamia nut oil, tung oil and the like. These may be used alone or in combination of two or more.

From the viewpoint of LCA (Life Cycle Assessment), it is preferable to use vegetable oil (plant-derived glycerol fatty acid triester) as the oil. Here, glycerol fatty acid triester is an ester of fatty acid and glycerin, and is also called triglyceride or tri-O-acylglycerin.

Fatty acids constituting the plant-derived glycerol fatty acid triester usually include palmitic acid (16 carbon atoms, 0 unsaturated bonds), stearic acid (18 carbon atoms, 0 unsaturated bonds), oleic acid (18 carbon atoms, , unsaturated bond number 1), and linoleic acid (carbon number 18, unsaturated bond number 2) are known to constitute the main components, and palmitic acid, stearic acid, oleic acid, linoleic acid in 100% by mass of constituent fatty acids The total acid content is usually 80% by mass or more, preferably 90% by mass or more.

The glycerol fatty acid triester preferably has a saturated fatty acid content of 10 to 25% by mass based on 100% by mass of the constituent fatty acids. The lower limit is more preferably 12% by mass or more, and the upper limit is more preferably 20% by mass or less, still more preferably 18% by mass or less, and particularly preferably 15% by mass or less.

In the glycerol fatty acid triester, the content of monounsaturated fatty acids having one unsaturated bond in 100% by mass of the constituent fatty acids is preferably less than 50% by mass, more preferably 45% by mass or less, and still more preferably. is 40% by mass or less, particularly preferably 35% by mass or less, and most preferably 30% by mass or less. Although the lower limit is not particularly limited, it is preferably 8% by mass or more, more preferably 14% by mass or more, and still more preferably 20% by mass or more.

In the glycerol fatty acid triester, the content of polyunsaturated fatty acids having two or more unsaturated bonds in 100% by mass of the constituent fatty acids is preferably 50% by mass or more, more preferably 55% by mass or more, and further Preferably, it is 60% by mass or more. Although the upper limit is not particularly limited, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

In the glycerol fatty acid triester, the content of divalent unsaturated fatty acids having two unsaturated bonds in 100% by mass of the constituent fatty acids is preferably 35 to 80% by mass, more preferably 40 to 70% by mass, and still more preferably. is 45 to 65% by mass. In addition, the content of trivalent unsaturated fatty acid having three unsaturated bonds in 100% by mass of constituent fatty acids is preferably 3 to 25% by mass, more preferably 5 to 15% by mass.

The glycerol fatty acid triester has a total unsaturated fatty acid content of preferably 75 to 90% by mass, more preferably 80 to 88% by mass, still more preferably 82 to 88% by mass, based on 100% by mass of the constituent fatty acids. It is preferably 85 to 88% by mass.

The glycerol fatty acid triester preferably satisfies the following formula (A).
The lower limit of the following formula (A) is preferably 100 or more, more preferably 120 or more, still more preferably 140 or more, particularly preferably 150 or more, and the upper limit is preferably 190 or less, more preferably 180 or less, and still more preferably is 170 or less.
80 ≤ Content of monounsaturated fatty acid having one unsaturated bond in 100% by mass of constituent fatty acid (% by mass) x 1 (number of unsaturated bonds) + 2 unsaturated bonds in 100% by mass of constituent fatty acid Content of divalent unsaturated fatty acids (% by mass) x 2 (number of unsaturated bonds) + content of triunsaturated fatty acids having 3 unsaturated bonds in 100% by mass of constituent fatty acids (% by mass) x 3 (Number of unsaturated bonds) ≤ 200 Formula (A)

When the glycerol fatty acid triester is a plant-derived glycerol fatty acid triester, the unsaturated bond of the constituent fatty acid is usually a double bond.

In the glycerol fatty acid triester, the average carbon number of constituent fatty acids is preferably 15-21, more preferably 16-20, still more preferably 17-19.
In the present specification, the average carbon number of constituent fatty acids is calculated by the following formula (D).
Average carbon number of constituent fatty acids = Content of fatty acids with carbon number n in Σ constituent fatty acids 100% by weight (% by mass) x n (carbon number) / 100 Formula (D)

The glycerol fatty acid triester is preferably liquid at room temperature (25°C). The melting point of the glycerol fatty acid triester is preferably 20° C. or lower, more preferably 17° C. or lower, still more preferably 0° C. or lower, and particularly preferably −5° C. or lower.
Although the lower limit is not particularly limited, it is preferably -100°C or higher, more preferably -90°C or higher.
The melting point of the glycerol fatty acid triester can be measured by differential scanning calorimetry (DSC).

The iodine value of the glycerol fatty acid triester is preferably 60 or higher, more preferably 70 or higher, even more preferably 80 or higher, particularly preferably 100 or higher, and most preferably 120 or higher. Also, the iodine value is preferably 160 or less, more preferably 150 or less, and even more preferably 135 or less.
In the present specification, the iodine value is obtained by converting the amount of halogen bonded to iodine in grams when 100 g of glycerol fatty acid triester is reacted with halogen. It is a measured value.

Vegetable oils (plant-derived glycerol fatty acid triesters) include, for example, the above-mentioned vegetable oils, and specific examples include those derived from soybean oil, sesame oil, rice oil, safflower oil, corn oil, olive oil, rapeseed oil, and the like. mentioned.

The fatty acid composition can be measured by GLC (gas-liquid chromatography).

As the oil, one obtained by saponifying vegetable oil (plant-derived glycerol fatty acid triester) (saponified vegetable oil) can also be suitably used. The saponification treatment can be carried out by adding an alkali to the above vegetable oil and allowing it to stand at a predetermined temperature for a certain period of time. In addition, you may perform stirring etc. as needed.

Alkali that can be used for the saponification treatment include sodium hydroxide, potassium hydroxide, calcium hydroxide, amine compounds, and the like. From the viewpoint of the effect of the saponification treatment, sodium hydroxide or potassium hydroxide is particularly used. is preferred.

The amount of alkali to be added is not particularly limited, but for example, the lower limit is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and still more preferably 1 part by mass or more with respect to 100 parts by mass of the vegetable oil. Moreover, the upper limit is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

The temperature of the saponification treatment can be appropriately set within a range in which the saponification reaction with alkali can proceed at a sufficient reaction rate and in a range in which the vegetable oil is not degraded. is more preferred. The treatment time is 30 minutes to 48 hours, depending on the temperature of the treatment when the vegetable oil is left to stand still, considering both the sufficient treatment and the improvement of productivity. Preferably, 1 to 24 hours is more preferable.

Commercially available products such as oils and glycerol fatty acid triesters are available from, for example, Idemitsu Kosan Co., Ltd., Sankyo Yuka Kogyo Co., Ltd., Japan Energy Co., Ltd., Orisoi Co., Ltd., H & R Co., Ltd., Toyokuni Oil Co., Ltd., Showa Shell Sekiyu. Co., Ltd., Fuji Kosan Co., Ltd., Nisshin OilliO Co., Ltd., J-Oil Mills Co., Ltd., Showa Sangyo Co., Ltd., Fuji Oil Co., Ltd., Miyoshi Oil Co., Ltd., Boso Oil Co., Ltd., etc. products can be used.

Step 3 of mixing the mixture 2 optionally dehydrated and a plasticizer to prepare the mixture 3 containing these components can be performed by a known mixing method, for example, the mixing method of step 1. A similar method can be adopted. The temperature and time during preparation can be appropriately set within the range usually performed, or can be adjusted as appropriate while measuring the viscosity so that the mixture has a desired viscosity. For example, the temperature is preferably 5 to 80°C, more preferably 10 to 50°C, even more preferably 12 to 40°C.

Among them, from the viewpoint of filler dispersibility, a method of mixing using a rotation-revolution mixing device is preferable. As used herein, the term "rotational mixing device" refers to a mixing device having both a rotation mechanism and a revolution mechanism, and examples thereof include a rotation and revolution stirrer and a planetary mixer.

A rotation/revolution stirrer is a device that stirs a material by revolving and rotating a container containing the material. Sufficient mixing becomes possible by centrifugal force, shearing force, etc. caused by revolving and rotating the container. For example, the stirrer described in JP-A-2015-52034, etc., and commercially available products include "Rotation/Revolution Mixer Awatori Rentaro ARE-310" manufactured by Thinky.

A planetary mixer is a planetary motion mixer that has blades (stirring blades) that have rotation and revolution functions as a stirring mechanism.

In the rotation/revolution stirrer and planetary mixer, the rotation speed and revolution rotation speed can realize good mixing by considering the amount of microfibrillated plant fiber, cationic surfactant containing cationic nitrogen, amount of water, etc. It should be set appropriately within the range.

In the step 3 of mixing the mixture 2 which has been optionally dehydrated and the plasticizer, the amount of the plasticizer to be added to 100 parts by mass (solid content) of the microfibrillated plant fibers is It is preferably within the range of 10 to 1000 parts by mass. The lower limit is more preferably 50 parts by mass or more, still more preferably 70 parts by mass or more, and particularly preferably 80 parts by mass or more. The upper limit is more preferably 500 parts by mass or less, still more preferably 300 parts by mass or less, and particularly preferably 200 parts by mass or less.

(Step 4)
In step 4, the mixture 3 obtained in step 3 is dried, thereby producing a composite (a composite containing microfibrillated plant fibers and a plasticizer) in which the microfibrillated plant fibers are well dispersed. .

Drying in step 4 can be performed using, for example, a known fluidized bed dryer. A "fluidized bed dryer" is a device that supplies warmed fluidizing air to a can body and dries a material to be treated that has been put into the interior while being fluidly circulated. In step 4, a fluidized bed dryer with an atomizing mechanism can be used.

As the spraying mechanism, for example, a jetting device such as a spray nozzle, a discharging device, or the like can be used. The ejection device and discharge device can be attached to the bottom, side, top, etc. of the fluidized bed provided in the apparatus, and can spray toward the fluidized bed. Spraying includes not only spraying toward the center of the fluidized bed, but also spraying by applying various methods. The fluidized bed dryer may also be a device equipped with a stirring/mixing/rolling mechanism typified by a stirring blade or a rotating disk in order to impart a stirring/rolling action to the powder.

As the fluidized bed dryer, for example, a known fluidized bed granulator dryer (fluidized bed granulator) can be suitably used from the viewpoint of obtaining more effects. The fluidized bed granulator dryer can use equipment commonly used for fluidized bed granulation. and a spray nozzle for spraying the liquid onto the object to be processed.

Among the fluidized bed granulator dryers, a composite fluidized bed granulator equipped with a jet flow, tumbling, agitation, pulse generating mechanism, etc. (rolling fluid bed granulation coating apparatus), a dryer equipped with a pulse generation mechanism (pulse fluidized bed granulation dryer) is more preferable, and a dryer equipped with a pulse generation mechanism is more preferable. In such a composite type fluidized bed granulator dryer, the granules are subjected to jet flow by means of forced circulation from the side of the fluidized bed, sizing and pulverization, rotation of the blade rotor in the fluidized bed, pulse generation mechanism, etc. , tumbling, agitation, periodic changes in wind speed, etc. are applied.

The fluidized bed dryer preferably introduces hot air into the fluidized bed as the drying air.
Regarding the treatment conditions during drying, the temperature of the hot air (air supply temperature) may be appropriately set in consideration of the components contained in the object to be treated, preferably 60 to 180 ° C., more preferably 70 to 150 ° C. , more preferably in the range of 80 to 120°C. The wind speed of the hot air (supply air volume) is preferably 0.1 to 3.0 m ³ /sec, more preferably 0.5 to 2.5 m ³ /sec, still more preferably 0.8 to 2.0 m ³ /sec. is.

The treatment time (drying time) in step 4 may be appropriately set in consideration of the components contained in the object to be treated, but is preferably 1 minute or longer, more preferably 5 minutes or longer, and still more preferably 7 minutes or longer. It is preferably 10 hours or less, more preferably 1 hour or less, and still more preferably 30 minutes or less.

The rate at which the mixture 3 is introduced into the fluidized bed dryer may be appropriately set in consideration of the spraying state, etc., but is preferably 1.0 g/min or more, more preferably 3.0 g/min or more, and still more preferably 5 g/min or more. 0 g/min or more, preferably 20.0 g/min or less, more preferably 10.0 g/min or less, and even more preferably 8.0 g/min or less.

Commercially available fluidized bed dryers include flow coater (manufactured by Freund Corporation), GPCG-CT series, WST/WSG series, BF series, PLS series (pulse fluidized bed granulation dryer), MP series (rolling flow granulation coating device) (manufactured by Powrex Corporation) and the like.

In the drying in step 4, the solid content of the composite (100% by mass) to be produced is preferably adjusted to 85% by mass or more, more preferably 90% by mass or more, still more preferably 92% by mass or more, especially Preferably, it is 94% by mass or more. The upper limit is not particularly limited, and may be 100% by mass. The term "solid content" refers to the content of solid components, such as microfibrillated plant fibers and plasticizers, in 100% by mass of the composite.

The composite produced in step 4 is preferably particles (powder) having an average particle size of 100 μm or less. The average particle size is more preferably 50 µm or less, still more preferably 30 µm or less, and particularly preferably 20 µm or less. Although the lower limit is not particularly limited, it is preferably 1 µm or more, more preferably 3 µm or more, and still more preferably 5 µm or more. Here, the particle size control of the granules (the support) produced using the fluidized bed dryer can be carried out by a method of adjusting the retention amount in the fluidized bed, a method of adjusting the position of the spray nozzle, and the like. .
In addition, in this specification, an average particle diameter is a number average particle diameter, and is measured with a transmission electron microscope.

<Complex>
A composite containing microfibrillated plant fibers and a plasticizer is obtained by the production method. The composite preferably has a solid content of 85% by mass or more in the composite (100% by mass), more preferably 90% by mass or more, still more preferably 92% by mass or more, and particularly preferably 94% by mass. % by mass or more. The term "solid content" refers to the content of solid components, such as microfibrillated plant fibers and plasticizers, in 100% by mass of the composite.

As a composite containing microfibrillated plant fibers and a plasticizer, for example, a powdery powder obtained by mixing the microfibrillated plant fibers having an average fiber diameter of 10 μm or less and the plasticizer and drying them. complexes. Such a powdery composite can be produced, for example, by the production method described above. Here, in the present specification, the term "powder" means a set of particles in which 90% by mass or more passes through a 75 μm (200 mesh) sieve.

From the viewpoint that a composite containing microfibrillated plant fibers and a plasticizer is more effective, the plasticizer contains vegetable oil and the content of microfibrillated plant fibers in the composite (100% by mass) (% by mass), the content of vegetable oil (% by mass), and the iodine value of the vegetable oil in the composite preferably satisfy the following formula.
Microfibrillated vegetable fiber content (mass%) / (vegetable oil content (mass%) × iodine value of vegetable oil) ≤ 0.0100
The upper limit is more preferably 0.0090 or less, even more preferably 0.0080 or less.
The lower limit is not particularly limited, and a smaller value is more desirable.

The composite is preferably particles (powder) having an average particle size of 100 μm or less. The average particle size is more preferably 50 µm or less, still more preferably 30 µm or less, and particularly preferably 20 µm or less. Although the lower limit is not particularly limited, it is preferably 1 µm or more, more preferably 3 µm or more, and still more preferably 5 µm or more.

<Rubber composition, resin composition>
The composite can be used as an additive for rubber compositions and resin compositions. By incorporating the composite into the composition, the microfibrillated plant fibers can be well dispersed in the composition, and the desired reinforcing effect can be imparted. Among others, it is desirable to blend the composite with the rubber composition.

(rubber composition)
In the rubber composition, the content of the microfibrillated plant fibers is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 7 parts by mass or more with respect to 100 parts by mass of the rubber component, and It is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 85 parts by mass or less.

Examples of the rubber component of the rubber composition include diene rubbers. Diene rubbers include isoprene rubber, butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR). ) and the like. In addition, butyl-based rubber, fluororubber, and the like can also be used. Among them, isoprene-based rubber, BR, and SBR are preferable from the viewpoint of tire physical properties.

The diene rubber may be non-modified diene rubber or modified diene rubber.
The modified diene rubber may be any diene rubber having a functional group that interacts with a filler such as silica. Terminal modified diene rubber modified with (terminal modified diene rubber having the above functional group at the end), main chain modified diene rubber having the above functional group on the main chain, and the above functional group on the main chain and terminal main chain end-modified diene rubber (for example, main chain end-modified diene rubber having the above functional group in the main chain and at least one end modified with the above modifier), or two or more in the molecule A terminal-modified diene rubber modified (coupled) with a polyfunctional compound having an epoxy group and introduced with a hydroxyl group or an epoxy group is exemplified.

Examples of the functional groups include amino group, amido group, silyl group, alkoxysilyl group, isocyanate group, imino group, imidazole group, urea group, ether group, carbonyl group, oxycarbonyl group, mercapto group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, ammonium group, imide group, hydrazo group, azo group, diazo group, carboxyl group, nitrile group, pyridyl group, alkoxy group, hydroxyl group, oxy group, epoxy group and the like. . In addition, these functional groups may have a substituent. Among them, an amino group (preferably an amino group in which the hydrogen atom of the amino group is substituted with an alkyl group having 1 to 6 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms), an alkoxysilyl group ( An alkoxysilyl group having 1 to 6 carbon atoms is preferred.

The isoprene rubber includes natural rubber (NR), isoprene rubber (IR), modified NR, modified NR, modified IR, and the like. As NR, for example, those commonly used in the tire industry, such as SIR20, RSS#3, and TSR20, can be used. The IR is not particularly limited, and for example IR2200 or the like commonly used in the tire industry can be used. Modified NR includes deproteinized natural rubber (DPNR), high-purity natural rubber (UPNR), etc. Modified NR includes epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), grafted natural rubber, etc. Examples of modified IR include epoxidized isoprene rubber, hydrogenated isoprene rubber, grafted isoprene rubber, and the like. These may be used alone or in combination of two or more.

In the rubber composition, the content of the isoprene-based rubber in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 95% by mass or less. , more preferably 90% by mass or less, and still more preferably 85% by mass or less.

The butadiene rubber (BR) is not particularly limited, and examples thereof include BR with a high cis content, BR containing 1,2-syndiotactic polybutadiene crystals (SPB-containing BR), and butadiene synthesized using a rare earth catalyst. Rubber (rare earth-based BR), tin-modified butadiene rubber modified with a tin compound (tin-modified BR), and other rubbers commonly used in the tire industry can be used. Commercially available BR products of Ube Industries, Ltd., JSR Corporation, Asahi Kasei Corporation, Zeon Corporation, etc. can be used. These may be used alone or in combination of two or more. BR may be unmodified BR or modified BR.

The cis content of BR is preferably 90% by mass or more, more preferably 95% by mass or more, from the viewpoint of good performance on ice and snow, abrasion resistance, and the like.
In this specification, the cis content (cis-1,4-bond amount) is a value calculated from signal intensity measured by infrared absorption spectroscopy or NMR analysis.

In the rubber composition, the content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 95% by mass or less, and more It is preferably 90% by mass or less, more preferably 85% by mass or less.

The SBR is not particularly limited, and for example, emulsion-polymerized styrene-butadiene rubber (E-SBR), solution-polymerized styrene-butadiene rubber (S-SBR), etc. can be used. These may be used alone or in combination of two or more.

The styrene content of SBR is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. Also, the styrene content is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
In this specification, the styrene content of SBR is calculated by ¹ H-NMR measurement.

The vinyl content of SBR is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. The vinyl content is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
The vinyl content (1,2-bonded butadiene unit amount) can be measured by infrared absorption spectrometry.

As SBR, for example, SBR manufactured and sold by Sumitomo Chemical Co., Ltd., JSR Co., Ltd., Asahi Kasei Co., Ltd., Nippon Zeon Co., Ltd., etc. can be used.

In the rubber composition, the content of SBR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 95% by mass or less. It is preferably 90% by mass or less, more preferably 85% by mass or less.

The rubber composition may contain a filler (filler). As the filler, inorganic fillers such as silica, carbon black, calcium carbonate, talc, alumina, clay, aluminum hydroxide, aluminum oxide and mica; hard-to-disperse fillers and other materials known in the rubber field can be used. Among them, carbon black and silica are preferred.

In the rubber composition, the total content of fillers (carbon black, silica, etc.) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more with respect to 100 parts by mass of the rubber component. is. The content is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and even more preferably 100 parts by mass or less.

Carbon black is not particularly limited, furnace blacks such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF (furnace carbon black); acetylene black (acetylene carbon black) thermal blacks (thermal carbon blacks) such as FT and MT; channel blacks (channel carbon blacks) such as EPC, MPC and CC; graphite. These may be used alone or in combination of two or more.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 30 m ² /g or more, more preferably 35 m ² /g or more, still more preferably 40 m ² /g or more. Although the upper limit is not particularly limited, it is preferably 250 m ² /g or less, more preferably 200 m ² /g or less, still more preferably 180 m ² /g or less.
The N ₂ SA of carbon black is determined according to JIS K 6217-2:2001.

In the rubber composition, the content of carbon black is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more with respect to 100 parts by mass of the rubber component. The content is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and even more preferably 100 parts by mass or less.

Examples of silica include dry silica (anhydrous silica) and wet silica (hydrous silica). These may be used alone or in combination of two or more. Among them, wet-process silica is preferable because it has many silanol groups.

The nitrogen adsorption specific surface area (N ₂ SA) of silica is preferably 40 m ² /g or more, more preferably 50 m ² /g or more, still more preferably 60 m ² /g or more. In addition, N ₂ SA of silica is preferably 250 m ² /g or less, more preferably 220 m ² /g or less, still more preferably 200 m ² /g or less. Within the above range, the effect tends to be obtained more favorably.
The N ₂ SA of silica is a value measured by the BET method according to ASTM D3037-93.

In the rubber composition, the content of silica is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more with respect to 100 parts by mass of the rubber component. The content is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and even more preferably 100 parts by mass or less.

As silica, for example, products of Degussa, Rhodia, Tosoh Silica, Solvay Japan, Tokuyama, etc. can be used.

The tread rubber composition preferably contains a silane coupling agent together with silica.
The silane coupling agent is not particularly limited, and examples thereof include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, Bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (2-triethoxysilylethyl) trisulfide, bis (4-trimethoxysilylbutyl) trisulfide, bis ( 3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) disulfide, bis(4-triethoxysilylbutyl) disulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(2-trimethoxysilylethyl) ) disulfide, bis(4-trimethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3- sulfides such as triethoxysilylpropyl methacrylate monosulfide; 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane; vinyl-based such as methoxysilane; amino-based such as 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane; glycidoxy-based such as γ-glycidoxypropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane; nitro-based such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane; and chloro-based such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane. These may be used alone or in combination of two or more. Among them, sulfide-based and mercapto-based are preferable because they are more effective.

Examples of silane coupling agents that can be used include products of Degussa, Momentive, Shin-Etsu Silicone Co., Ltd., Tokyo Chemical Industry Co., Ltd., Azmax Co., Ltd., Dow Corning Toray Co., Ltd., and the like.

In the rubber composition, the content of the silane coupling agent is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of silica. The content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

The rubber composition may contain other plasticizers in addition to the plasticizers used in the manufacturing method described above. Examples of plasticizers include those mentioned above. Specifically, examples of the liquid plasticizer include those described above. Examples of solid plasticizers include aromatic vinyl polymers, coumarone-indene resins, coumarone resins, indene resins, phenolic resins, rosin resins, petroleum resins, terpene-based resins, and acrylic resins that are in a solid state at room temperature (25°C). etc. Also, the resin may be hydrogenated. These may be used alone or in combination of two or more.

In the rubber composition, the total amount of the plasticizer (the total amount of the plasticizer in the composite and the separately blended plasticizer) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the rubber component. , more preferably 7 parts by mass or more. The upper limit is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.

The rubber composition preferably contains an antioxidant.
Antiaging agents are not particularly limited, but naphthylamine antiaging agents such as phenyl-α-naphthylamine; diphenylamine antiaging agents such as octylated diphenylamine and 4,4′-bis(α,α′-dimethylbenzyl)diphenylamine. ; N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylene p-phenylenediamine antioxidants such as diamines; quinoline antioxidants such as polymers of 2,2,4-trimethyl-1,2-dihydroquinoline; 2,6-di-t-butyl-4-methyl monophenol antioxidants such as phenol and styrenated phenol; bis, tris and polyphenols such as tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane anti-aging agent, etc. Among them, p-phenylenediamine-based antioxidants and quinoline-based antioxidants are preferable, and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 2,2,4-trimethyl-1 , 2-dihydroquinoline polymers are more preferred. As commercially available products, for example, products of Seiko Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., Ouchi Shinko Kagaku Kogyo Co., Ltd., Flexis, etc. can be used.

In the rubber composition, the content of the antioxidant is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the rubber component. The content is preferably 7.0 parts by mass or less, more preferably 4.0 parts by mass or less.

The rubber composition may contain stearic acid. In the rubber composition, the stearic acid content is preferably 0.5 to 10 parts by mass or more, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the rubber component.

As the stearic acid, conventionally known ones can be used, for example, products of NOF Corporation, Kao Corporation, FUJIFILM Wako Pure Chemical Industries, Ltd., Chiba Fatty Acids Co., Ltd., etc. can be used.

The rubber composition may contain zinc oxide. In the rubber composition, the zinc oxide content is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.

As the zinc oxide, conventionally known ones can be used. products can be used.

Wax may be blended in the rubber composition. In the rubber composition, the wax content is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.

The wax is not particularly limited, and examples thereof include petroleum waxes and natural waxes. Synthetic waxes obtained by refining or chemically treating a plurality of waxes can also be used. These waxes may be used alone or in combination of two or more.

Examples of petroleum wax include paraffin wax and microcrystalline wax. The natural wax is not particularly limited as long as it is derived from a resource other than petroleum. Examples include plant waxes such as candelilla wax, carnauba wax, Japan wax, rice wax, and jojoba wax; beeswax, lanolin, spermaceti, and the like. animal waxes; mineral waxes such as ozokerite, ceresin and petrolactam; and refined products thereof. As commercially available products, for example, products of Ouchi Shinko Kagaku Kogyo Co., Ltd., Nippon Seiro Co., Ltd., Seiko Kagaku Co., Ltd., etc. can be used.

The rubber composition may contain sulfur.
In the tread rubber composition, the sulfur content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 0.7 parts by mass or more, relative to 100 parts by mass of the rubber component. is. The content is preferably 6.0 parts by mass or less, more preferably 4.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.

Sulfur includes powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, soluble sulfur and the like commonly used in the rubber industry. As commercially available products, products of Tsurumi Chemical Industry Co., Ltd., Karuizawa Io Co., Ltd., Shikoku Kasei Kogyo Co., Ltd., Flexis Co., Ltd., Nippon Kantan Kogyo Co., Ltd., Hosoi Chemical Industry Co., Ltd., etc. can be used. These may be used alone or in combination of two or more.

The rubber composition may contain a vulcanization accelerator.
In the tread rubber composition, the content of the vulcanization accelerator is usually 0.3 to 10 parts by mass, preferably 0.5 to 7 parts by mass, per 100 parts by mass of the rubber component.

The type of vulcanization accelerator is not particularly limited, and commonly used ones can be used. Vulcanization accelerators include thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram disulfide (TMTD ), tetrabenzyl thiuram disulfide (TBzTD), tetrakis (2-ethylhexyl) thiuram disulfide (TOT-N) and other thiuram vulcanization accelerators; N-cyclohexyl-2-benzothiazolesulfenamide, Nt-butyl- Sulfenamide-based vulcanization accelerators such as 2-benzothiazolylsulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N,N'-diisopropyl-2-benzothiazolesulfenamide; diphenylguanidine, Guanidine-based vulcanization accelerators such as dioltolylguanidine and orthotolylbiguanidine can be mentioned. These may be used alone or in combination of two or more. Among them, sulfenamide-based vulcanization accelerators and guanidine-based vulcanization accelerators are preferred.

In the rubber composition, the content of the vulcanization accelerator is preferably 0.3 to 4.0 parts by mass, preferably 0.5 to 2.5 parts by mass, more preferably 100 parts by mass of the rubber component. 0.7 to 1.6 parts by mass.

As a method for producing the rubber composition, a known method can be used, and examples thereof include a production method including a step of mixing the composite with a rubber component. Specifically, for example, each component such as the composite and the rubber component is kneaded using a rubber kneading device such as an open roll or Banbury mixer, and then vulcanized.

As kneading conditions, in the base kneading step in which additives other than the vulcanizing agent and the vulcanization accelerator are kneaded, the kneading temperature is usually 50 to 200°C, preferably 80 to 190°C, and the kneading time is usually 30°C. seconds to 30 minutes, preferably 1 minute to 30 minutes. In the finishing kneading step of kneading the vulcanizing agent and the vulcanization accelerator, the kneading temperature is usually 100°C or lower, preferably room temperature to 80°C. A composition obtained by kneading a vulcanizing agent and a vulcanization accelerator is usually subjected to vulcanization treatment such as press vulcanization. The vulcanization temperature is generally 120-200°C, preferably 140-180°C.

The rubber composition can be suitably applied as a tire member.
The tire member is not particularly limited, and includes arbitrary tire members such as cap tread, sidewall, base tread, bead apex, clinch apex, inner liner, under tread, breaker topping, and ply topping.

It is preferable that the tire member is obtained by extruding the rubber composition obtained by the manufacturing method described above, and the microfibrillated plant fibers are oriented in the direction of extrusion. In this case, an excellent reinforcing effect can be imparted to the tire member.

Examples of tires include pneumatic tires and non-pneumatic tires. Among them, pneumatic tires are preferred. For example, it can be suitably used as summer tires (summer tires) and winter tires (studless tires, snow tires, stud tires, etc.). Tires can be used as tires for passenger cars, tires for large passenger cars, tires for large SUVs, tires for heavy loads such as trucks and buses, tires for light trucks, tires for two-wheeled vehicles, tires for racing (high performance tires), and the like.

A tire is manufactured by a conventional method using a rubber composition containing the above composite. That is, a rubber composition blended with various additives as necessary is extruded in the unvulcanized stage according to the shape of a tire member, molded by a normal method on a tire molding machine, and other After forming an unvulcanized tire by laminating together with the tire member, the tire can be manufactured by heating and pressurizing in a vulcanizer.

(resin composition)
When the composite is used as an additive for a resin composition, examples of the resin composition include those containing a dispersing resin and the composite.

The dispersing resin is not particularly limited and includes known resins. Examples thereof include petroleum-based resins, coal-based resins, terpene-based resins, and rosin-based resins. is more preferred.

Petroleum-based resins include, for example, C5-based petroleum resins, C9-based petroleum resins, C5C9-based petroleum resins, dicyclopentadiene resins, hydrides thereof, and cyclic polybasic acid anhydrides (e.g., maleic anhydride acid) (grafting) is added. Among them, C9 petroleum resins are preferred.

Examples of the coal-based resin include coumarone resin, coumarone-indene resin, hydrides thereof, and modified products obtained by (grafting) addition of cyclic polybasic acid anhydride (e.g., maleic anhydride) thereto. mentioned.

Examples of the terpene resin include α-pinene resin, β-pinene resin, terpene phenol resin, aromatic modified terpene resin, hydrides thereof, and modified products obtained by adding maleic anhydride thereto. .

Examples of the rosin-based resin include gum rosin, wood rosin, tall rosin, hydrogenated rosin made from the above rosin, disproportionated rosin, maleic acid-modified rosin, fumaric acid-modified rosin, (meth)acrylic acid-modified rosin, and alcohol. esterified rosin condensed with and phenol-modified rosin.

The dispersing resin preferably has a softening point of 135° C. or less in a ring and ball test according to JIS K2207. The softening point is preferably 120° C. or lower, more preferably 110° C. or lower. On the other hand, the softening point is preferably 40°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher.

In the resin composition, the content of the microfibrillated plant fibers is preferably 1 part by mass or more, more preferably 5% by mass or more, and still more preferably 7 parts by mass or more, relative to 100 parts by mass of the dispersing resin, and , preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 85 parts by mass or less.

The resin composition can be produced by a known method, for example, by a known kneading method. Usable kneaders include a two-roll mill, a three-roll mill, a single-screw extrusion kneader, a twin-screw extrusion kneader, a Banbury mixer, a pressure kneader, and the like.

The resin composition can be molded into various shapes for use. Examples of the shape include sheet, film, pellet, powder, and the like. Molding materials having these shapes can be obtained by, for example, press molding, injection molding, extrusion molding, blow molding, stretch molding, foam molding, transfer molding, laminate molding, cast molding, and the like.

The molding material may optionally contain lubricants, waxes, colorants, stabilizers, fillers, and other various additives.

Molded bodies made from molding materials are, for example, interior materials, exterior materials, structural materials, etc. of transportation equipment such as automobiles, trains, ships, and airplanes; Materials, internal parts, etc.; Housings, structural materials, internal parts, etc. of mobile communication devices such as mobile phones; etc.; building materials; office equipment such as stationery;

EXAMPLES The present invention will be specifically described based on Examples, but the present invention is not limited to these.

Various chemicals used in Examples and Comparative Examples are described below.

Microfibrillated plant fiber: Biomass nanofiber manufactured by Sugino Machine Co., Ltd. (product name “BiNFi-s cellulose”, solid content 2% by mass, water content 98% by mass, average fiber diameter 20 to 50 nm, average fiber length 500 to 1000 nm )
TEMPO: 2,2,6,6-tetramethylpiperidine-1-oxyl Sodium bromide: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Sodium hypochlorite: manufactured by Tokyo Chemical Industry Co., Ltd. NaOH: FUJIFILM Wako Pure Chemical Industries, Ltd. Cationic surfactant having cationic nitrogen (manufactured by Co., Ltd.) 1: Kotamine 86P (stearyltrimethylammonium chloride) manufactured by Kao Corporation
Cationic surfactant having cationic nitrogen 2: Kao Co., Ltd. Kotamine 60W (cetyltrimethylammonium chloride)
Canola oil: Canola oil manufactured by Nisshin OilliO Co., Ltd. (composition shown in Table 1)
Corn oil: Nisshin OilliO Co., Ltd. corn oil (composition as shown in Table 1)
Palm oil: Palm oil manufactured by Nisshin OilliO Co., Ltd. (composition shown in Table 1)
Flaxseed oil: Flaxseed oil manufactured by Nisshin OilliO Co., Ltd. (composition shown in Table 1)
Aroma oil: Diana Process AH-24 (aromatic process oil) manufactured by Idemitsu Kosan Co., Ltd.
SBR: Nipol 1502 (E-SBR, styrene content 23.5% by mass) manufactured by Nippon Zeon Co., Ltd.
Carbon black: Diablack N220 (N ₂ SA111 m ² /g) manufactured by Mitsubishi Chemical Corporation
Silica: Ultrasil VN3 from Evonik Degussa (N ₂ SA 175 m ² /g)
Silane coupling agent: Si266 (bis(3-triethoxysilylpropyl) disulfide) manufactured by Evonik Degussa
TEMPO-oxidized CNF: preparation of the following microfibrillated plant fiber dispersion anti-aging agent: Nocrack 6C (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylene manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) diamine)
Zinc oxide: zinc oxide No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: stearic acid "Tsubaki" manufactured by NOF Corporation
Sulfur: Hosoi Chemical Industry Co., Ltd. HK-200-5 (powder sulfur containing 5 mass% oil)
Vulcanization accelerator: Noxceler CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.

(Preparation of Microfibrillated Plant Fiber Dispersion (Nanoized Cellulose Dispersion))
After dispersing 10 g of microfibrillated plant fibers, 150 mg of TEMPO, and 1000 mg of sodium bromide in 1000 ml of water, 15% by mass of sodium hypochlorite aqueous solution was added to 1 g of microfibrillated plant fibers (absolutely dry). The reaction was initiated by adding sodium phosphate in an amount of 5 mmol. During the reaction, a 3M NaOH aqueous solution was added dropwise to keep the pH at 10.0. When the pH no longer changes, the reaction is considered to be completed. After filtering the reactant with a glass filter, washing with a sufficient amount of water and filtering are repeated 5 times, and the product is impregnated with water having a solid content of 15% by mass. A reactant fiber (TEMPO-oxidized CNF, average fiber diameter of 10 μm or less) was obtained.

<Production of mixtures 1-1 to 1-2>
1990 g of pure water was added to 10 g (solid content) of the obtained TEMPO-oxidized CNF to prepare a 0.5% by mass (solid content concentration) suspension of TEMPO-oxidized CNF, and a high-speed homogenizer ("T25" manufactured by IKA Japan Co., Ltd. , rotation speed: 10000 rpm) for about 5 minutes to prepare a uniform aqueous dispersion.
According to the formulation in Table 2, the cationic surfactants 1 and 2 having cationic nitrogen are added to the water dispersion prepared above (in terms of the dry mass (solid content) of TEMPO-oxidized CNF), and a high-speed homogenizer (IKA Japan) is used. Company "T25", rotation speed: 10000 rpm), stir and mix for 5 minutes at 50 ° C., and mix 1-1 to 1-2 (solid content: about 0.5% by mass, moisture content: about 99.5% by mass) was prepared.

<Dehydration>
Using a suction filtration device, the resulting mixtures 1-1 to 1-2 were dehydrated for 30 minutes to adjust the solid content, and the dehydrated mixtures 1-1 to 1-2 (solid content : about 10% by mass, moisture content: about 90% by mass).

<Production of mixtures 2-1 to 2-2>
Add 500 ml of ethanol to 100 g of the dehydrated mixture 1-1 to 1-2 (solid content: about 10% by mass, moisture content: about 90% by mass), and use a high-speed homogenizer ("T25" manufactured by IKA Japan). , rotation speed: 10000 rpm) at 50° C. for 5 minutes to prepare mixtures 2-1 and 2-2.

<Dehydration>
Using a suction filtration device, the resulting mixtures 2-1 to 2-2 were dehydrated for 15 minutes to adjust the solid content rate, and the dehydrated mixtures 2-1 to 2-2 (solid content rate : about 20% by mass, liquid fraction: about 80% by mass).

<Production of mixtures 3-1 to 3-9>
According to the formulation shown in Table 3, 10 g of vegetable oil or aromatic oil was added to the dehydrated mixtures 2-1 to 2-2 (solid content: about 20% by mass, liquid content: about 80% by mass). Stirred and mixed at 50 ° C. for 5 minutes using a revolution stirrer (“Thinky Mixer ARV-310” manufactured by Thinky, stirring conditions: revolution rotation speed 1000 rpm, autorotation rotation speed 400 rpm), and mixtures 3-1 to 3 -9 was prepared.

<Drying process>
The resulting mixtures 3-1 to 3-9 were granulated and dried using the following fluidized bed dryer under the following conditions to obtain composites 1 to 9. Table 4 shows the physical properties of Composites 1 to 9.
(Equipment used)
Pulse fluidized bed granulator dryer (manufactured by Powrex Co., Ltd., PLS-01 model)
(conditions)
Mixed amount: 300g
Air supply temperature: 95°C
Air supply air volume: 0.9 m ³ /min Drying time: 10 minutes

A mixture containing TEMPO-oxidized CNF and vegetable oil was dried using a pulse fluidized bed granulator to obtain an entangled fibrous composite (powder composite). It was also found that the resulting complex was prevented from aggregating. Therefore, it was possible to produce a composite with excellent dispersibility of microfibrillated plant fibers by a simple production method that is significantly different from the WMB method.

<Production of rubber composition>
According to the formulation shown in Table 5, using a 1.7 L Banbury mixer, materials other than sulfur and a vulcanization accelerator were kneaded at 150° C. for 4 minutes. Next, using an open roll, sulfur and a vulcanization accelerator were added to the resulting kneaded material and kneaded at 80° C. for 4 minutes to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press-vulcanized at 170° C. for 12 minutes in a mold having a thickness of 2 mm to obtain a vulcanized rubber composition.

The obtained vulcanized rubber compositions were evaluated by the following methods. Comparative Example 1 was used as the reference comparative example in Table 5.
〔Evaluation method〕
(Dispersibility of microfibrillated plant fibers)
The vulcanized rubber composition was observed under an electron microscope to evaluate the dispersibility of the microfibrillated plant fibers in the rubber matrix. Taking the dispersibility of the microfibrillated plant fibers of the reference comparative example as 100, each compounded rubber was indicated as an index. A larger index indicates better dispersibility of microfibrillated plant fibers.

(Breaking strength)
A No. 3 dumbbell-shaped rubber test piece was prepared using the vulcanized rubber composition, and a tensile test was performed according to JIS K6251 "Vulcanized rubber and thermoplastic rubber-How to determine tensile properties", and the breaking strength (TB) was measured. It was measured. Taking the TB index of the rubber test piece of the standard comparative example (reference test piece) as 100, the TB of each formulation was indicated by the following formula. The larger the TB index, the higher the breaking strength and the better the reinforcing properties.
(TB index) = (TB of each formulation) / (TB of reference comparative example) x 100

From Table 5, Examples 1 to 9 using Composites 1 to 9 had good dispersibility of the microfibrillated plant fibers and were able to impart excellent reinforcing properties.

Claims (17)

Step 1 of mixing microfibrillated plant fibers, a cationic surfactant having cationic nitrogen and water to prepare a mixture 1;
Step 2 of mixing the mixture 1 and alcohol to prepare a mixture 2;
Step 3 of mixing the mixture 2 and a plasticizer to produce a mixture 3;
and a step 4 of drying the mixture 3 to produce a composite comprising the microfibrillated plant fibers and the plasticizer. 2. The method for producing a composite according to claim 1, wherein said step 1 uses an aqueous microfibrillated plant fiber solution having a microfibrillated plant fiber content of 0.1 to 20% by mass and is mixed using a homogenizer. 3. The method for producing a composite according to claim 1, wherein after step 1, dehydration under reduced pressure is further performed using a suction filtration device to adjust the solid content of the mixture 1 to 10% by mass or more. 4. The method for producing a composite according to any one of claims 1 to 3, wherein after step 2, dehydration under reduced pressure is further performed using a suction filtration device to adjust the solid content of the mixture 2 to 20% by mass or more. The method for producing a composite according to any one of claims 1 to 4, wherein the plasticizer contains a glycerol fatty acid triester. The method for producing a composite according to any one of claims 1 to 5, wherein the step 4 adjusts the solid content of the obtained composite to 90% by mass or more. 7. Any one of claims 1 to 6, wherein in step 1, the amount of the cationic surfactant having cationic nitrogen added to 100 parts by mass (solid content) of the microfibrillated plant fibers is 10 to 35 parts by mass. A method of making the described composite. The method for producing a complex according to any one of claims 1 to 7, wherein the cationic surfactant having a cationic nitrogen contains at least one selected from the group consisting of quaternary ammonium salts and alkylamine salts. . 9. The method for producing a composite according to any one of claims 1 to 8, wherein in step 2, the alcohol is added in an amount of 2,000 to 10,000 parts by mass with respect to 100 parts by mass (solid content) of the microfibrillated plant fibers. 10. The method for producing a composite according to any one of claims 1 to 9, wherein in the step 3, the amount of the plasticizer added to 100 parts by mass (solid content) of the microfibrillated plant fibers is 70 to 300 parts by mass. A powdery composite obtained by mixing and drying microfibrillated plant fibers having an average fiber diameter of 10 μm or less and a plasticizer. 12. The composite of claim 11, wherein said plasticizer comprises vegetable oil. 13. The composite according to claim 11 or 12, wherein the plasticizer contains a vegetable oil having an iodine value of 60 or more and 160 or less. A composite according to any one of claims 11 to 13, wherein said plasticizer comprises vegetable oil and satisfies the following formula:
Microfibrillated vegetable fiber content (mass%) / (vegetable oil content (mass%) × iodine value of vegetable oil) ≤ 0.0100 The composite according to any one of claims 11 to 14, which is an additive for a rubber composition or a resin composition. A rubber composition for tires in which the composite according to any one of claims 11 to 15 and a rubber component are mixed. A tire comprising a member made of the rubber composition according to claim 16 .